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Fluoride Removal from Water by Chitosan

Derivatives and Composites
Article in Journal of Fluorine Chemistry April 2011
DOI: 10.1016/j.jfluchem.2011.02.001

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Accepted Manuscript
Title: Fluoride removal from water by chitosan derivatives and
composites: a review
Authors: Patricia Miretzky, Alicia Fernandez Cirelli
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doi:10.1016/j.jfluchem.2011.02.001
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Please cite this article as: P. Miretzky, A.F. Cirelli, Fluoride removal from water by
chitosan derivatives and composites: a review, Journal of Fluorine Chemistry (2010),
doi:10.1016/j.jfluchem.2011.02.001
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Fluoride removal from water by chitosan derivatives and composites: a review

Patricia Miretzky a,*, Alicia Fernandez Cirelli b
a

Centro de Geociencias-Universidad Nacional Autnoma de Mxico, Campus Juriquilla, Boulevard Juriquilla 3001,

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Queretaro, Mexico (76230).

Centro de Estudios Transdisciplinarios del Agua, Facultad de Ciencias Veterinarias, Universidad de Buenos Aires.

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Chorroarn 280, Buenos Aires. Argentina (1427).

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Abstract

Fluoride is an essential element, indispensable for maintenance of dental health. Nevertheless,

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fluoride concentrations in drinking water above 1.5 mg L-1 may be detrimental to human health.
Many methods have been developed for removing excessive fluoride from drinking water,

adsorption seems to be an effective, environmentally friendly and economical one. Since the
sorption capacity of fluoride below 2 mg L-1 on most conventional adsorbents is not satisfactory,

much effort has been devoted to develop new and cost-effective fluoride adsorbents. This review
reports the recent developments in the F- removal in water treatment, using chitosan derivatives

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and composites in order to provide useful information about the different technologies. When

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possibly the adsorption capacity of chitosan derivatives and composites under different
experimental conditions is reported to help to compare the efficacy of the fluoride removal
process. A comparison with the adsorption capacity of other low cost adsorbents is also tabled.
Keywords: Fluoride removal; chitosan derivatives; chitosan composites; rare earth metals

*Corresponding author. Tel: + 52 442 2381104 ext. 132; fax: +52 442 2381100
E-mail address: patovior@geociencias.unam.mx (Patricia Miretzky)

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1. Introduction

Fluoride is an essential element, indispensable for maintenance of dental health. Nevertheless,

fluoride concentrations in drinking water above 1.5 mg L-1 may be detrimental to human health,

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leading to dental or skeletal fluorosis. The World Health Organization (WHO) has set a desirable
and permissible limit range between 0.5 and 1.0 mg L-1 in drinking water [1].

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Fluorosis is endemic in many parts of the world, particularly in mid latitude regions. Ground
water with high fluoride concentrations occurs in large parts of Africa, China, the Middle East,

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southern Asia (India and Sri Lanka), United States, Mexico, Chile and Argentina [2-4].
Increasing amount of wastewater containing fluoride is being released from various engineering

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processes, such as semiconductor manufacturing, coal power plants, electroplating, rubber and
fertilizer production, etc [5].

Many methods have been developed for removing excessive fluoride from drinking water,

such as the use of ion exchange columns, coagulation, use of membranes, electrochemical
methods, but the high cost of these technologies makes them unpractical for developing

countries. Excellent reviews of different technologies for the defluoridation of drinking water are

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those of Ayoob et al. [6] and Mohapatra et al. [7]. Among these techniques, adsorption seems to
be an effective, environmentally friendly and economical one. Different adsorbents have been

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used for F removal, among them, activated alumina [8-10], titanium rich bauxite [11], synthetic
resins [12], manganese oxide-coated alumina [13], carbon nanotubes [14,15], bone char [16],
double layered hydroxides [17], kaolinite [18], etc. Activated alumina is the most common
sorbent widely used for defluoridation of drinking water, but its optimal adsorption often works
at low pH values, fact that increases dissolved aluminum in treated water [19]. Since the sorption
capacity of fluoride on most conventional adsorbents is not satisfactory, and since a large
number of materials that have been tested at relatively high fluoride concentrations displayed a
very low capacity of fluoride removal below 2 mg L-1 [20], much effort has been devoted in
recent years, to develop new and cost-effective fluoride adsorbents.
The use of adsorbents containing natural polymers has received great attention, in particular
polysaccharides such as chitin and its derivate chitosan. Chitin is the second most abundant
natural biopolymer after cellulose and the most abundant amino polysaccharide. It is found in

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the shells of crustaceans, shells and skeletons of mollusks and krill, on the exoskeletons of some
arthropods and in the cell walls of some fungi [21,22].
Chitosan, a copolymer that is primarily composed of (14) linked 2-amino-2-deoxy-Dglucopyranose units, and residual 2-acetamido-2-deoxy-D-glucopyranose units, is a chemical

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derivative obtained by alkaline deacetylation of chitin and also it is found naturally in some
fungal cell walls. Since it is harmless to humans and presents excellent biological properties such

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as biodegradation in the human body, immunological, antibacterial, and wound-healing activity

[23], chitosan has been widely used in food and pharmaceutical processes and in medical and

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agricultural drugs [24,25].

Chitosan is well known as an excellent biosorbent for metal cation removal in near- neutral
solutions because the large number of NH2 groups. Excellent reviews on metal complexation by

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chitosan are those of Varma et al. [26], Crini [27] and Kurita [28]. Also, due to its cationic
behavior, in acidic media, the protonation of amine groups leads to adsorption of metal anions by

ion exchange [29-33].

Several methods have been used to modify natural chitosan either physically or chemically in

order to improve the adsorption capacity. Chitosan naturally occurs in the form of flakes or
powder which have limited utility particularly for column applications due to swelling, low

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mechanical strength, crumbling, etc. Attempts have been made to overcome these drawbacks
through formation of chitosan beads through various routes [34].

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Crosslinking with glutaraldehyde (GLA) or epichlorohydrin (ECH) can be cited as examples

of chitosan chemical modifications. These reactions are done in order to prevent its dissolution in
acidic solutions or to improve metal sorption properties (to increase sorption capacity and/or to
enhance sorption selectivity) [35]. It must be taken into account that crosslinking can reduce the
adsorption capacity as it diminishes the quantities of free amino groups, but this loss of capacity
may be necessary to ensure stability of the polymer. The adsorption capacity of chitosan varies
with porosity, crystallinity, affinity for water, percent deacetylation and the related amino group
content [36].
Chitosan can be molded in several shapes, membranes, micro-spheres, gel beads, films,
nanoparticles and nanofibers [37-39], and is able to provide a ratio: surface area/mass that
maximizes the adsorption capacity and minimizes the hydrodynamic limitation effects, such as
column clogging and friction loss [40]. Due to these facts, some authors have studied several
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ways to support chitin and chitosan by means of synthetic materials such as polymers. Polymeric
supports have advantages such as easy handling and versatility. Also it is possible to obtain
homogeneous, porous, malleable and mechanically-chemically resistant biocomposites.
However, at the same time, their sorption capacity is reduced due to blockage of adsorption sites

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by the physical and chemical interactions between the supporting media and the biopolymer [41].
Different mineral materials as hydroxyapatite, binary metal oxides, magnesia, hydrotalcite,

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alumina, rare earth metals, etc. have been supported on chitosan resulting in inorganic
composites with high F removal capacity [42-56] etc.

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The aim of this study is to review the literature in order to provide useful information about
the different technologies for F removal from solution using chitosan and its derivatives and

2. Physicochemical characteristics of chitosan

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when possibly to report the adsorption capacity under different experimental conditions.

Chitosan, poly- (1-4)-2-amino-2-deoxy-D-glucopyranose is a polysaccharide obtained by

partial or total N-deacetylation of chitin poly- (1-4)-2-acetamide-2-deoxy-D-glucopyranose.

The difference between chitin and chitosan is the deacetylation degree and their respective

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solubility in dilute acidic media. Chitosan is the only derivative soluble at a degree of
deacetylation above 40 % [57]. Although the polymer backbone consists of hydrophilic

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functional groups, chitosan is normally insoluble in water at near neutral pH and most common
organic solvents (e.g. DMSO, DMF, NMP, organic alcohols, pyridine). The insolubility of
chitosan in aqueous and organic solvents is a result of its crystalline structure, which is attributed
to extensive intramolecular and intermolecular hydrogen bonding between the chains and sheets,
respectively [58].

The degree of deacetylation depends on the raw material from which chitin was obtained and
the experimental procedure, and controls the fraction of free amino groups that will be available
for interactions with metals ions [35].When the degree of deacetylation of chitin is larger than
40-50 %, chitosan becomes soluble in acidic media. The solubilization occurs by protonation of
the NH2 groups on the C2 position of the D-glucosamine unit, although the distribution of acetyl
groups along the chain may modify solubility [59]. The presence of amino groups makes
chitosan a cationic polyelectrolyte (pKa = 6.5), one of the few found in nature.

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Chitosan can be modified by chemical or physical processes in order to improve the

mechanical and chemical properties. The efficiency of adsorption depends on physicochemical
properties, mainly surface area, porosity and particle size of adsorbents. Chitosan has a very low
specific area ranging between 2 and 30 m2 g-1 whereas most commercial activated carbons range

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between 800 to 1500 m2 g-1 [27]. Chitosan based material are used in different fields of
application in the form of powder, flakes and foremost as gels: beads, membranes, sponge,

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fibers, hollow fibers, etc, [60,61]. Flake and power forms of chitosan are not suitable to be used
as adsorbents due to their low surface area and no porosity [26]. Chitosan flakes modified into
describing the preparation of chitosan gels [62,63].

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beads are essential for the enhancement of adsorption performance [35]. There are many studies
The chemical modification of chitosan is of special interest when this modification does not

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change the fundamental skeleton of chitosan but brings new or improved properties. A great
number of chitosan derivatives have been obtained by grafting new functional groups on the

chitosan backbone to increase the metal adsorption capacity. The new functional groups are
incorporated to increase the density of sorption sites, to change the pH range for metal sorption

and to change the sorption sites in order to increase sorption selectivity for the target metal [28].
The chemical modification affords a wide range of derivatives with modified properties for
biotechnological fields [64].

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specific use and applications in diversified areas mainly of pharmaceutical, biomedical and

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Cross linking agents are generally composed by functional groups separated by some spaced
molecules that can be structured in various forms (rings, straight chains, branched chains). The
crosslinking agents can be of varying length and contain other functional groups than those
involved in cross linking. Partial crosslinking by di/polyfunctional reagents enables the use of
chitosan for metal adsorption in acidic medium. In a general way, the adsorption capacity
decreases with the extent of crosslinking as it diminishes the reactive sites on the chitosan
polymer but also, it can improve the adsorption capacity, depending on the functional groups in
the crosslinking agent [65], being the most common, glutaraldehyde (GLA), ethylene glycol
diglycidyl ether (EGDE) and epichlorohydrin (EPI).

3. Characterization of chitosan and chitosan derivatives

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The identification of chitosan and chitosan derivatives has been carried out by different non
destructive techniques (Table1) : X-ray diffraction (XRD) [46,48,49,66], scanning electron
microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) [47,66-69], Fourier
transform infrared spectroscopy (FTIR) [44,45,48,49,70]. Excellent reviews on description and

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discussion of the different techniques mentioned above can be seen elsewhere [71-73].

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4. Fluoride detection

Fluoride analysis has been carried out by the fluoride selective electrode method (ASTM

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D1179-B). TISAB (III) solution was used as a buffer for maintaining the pH and background ion
concentrations [43-56,66-70,74,75]. Also fluoride concentration determination was carried on

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using zirconyl-SPADNS dye and UV-Vis spectrophotometer (EPA 340.1 method) by Kamble et
al. [42].

5. Fluoride sorption studies

5.1. Chitosan and chitosan modified materials

shown in Table 1.

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Results on F- adsorption onto chitosan and chitosan derivatives from different researchers are

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Defluoridation studies on natural chitosan were performed by Menkouchi Sahli et al. [75].
Batch experiments were carried out under different experimental conditions. The adsorption data
were fitted to Langmuir and Freundlich isotherms. The maximum adsorption capacity reported
was 1.39 mg g-1.

Carboxylated cross- linked chistosan beads (CCB) were investigated as F- adsorbent material
[67]. The chitosan beads were crosslinked with glutaraldehyde. In order to effectively utilize the
hydroxyl groups of chitosan and in this way enhance the defluoridation capacity, the carboxylic
group was introduced using chloroacetic acid. Batch experiments were performed under different
experimental condition to investigate the F- removal capacity of CCB. The defluoridation
capacity was not influenced by the pH of the medium and slightly affected in the presence of coanions. Adsorption data were fitted to Langmuir and Freundlich isotherms. The maximum
adsorption capacity was 11.11 mg g -1. The nature of the F- adsorption process was spontaneous
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and endothermic. The rate of F- adsorption reaction followed pseudo second order kinetic and
intraparticle diffusion models. The mechanism proposed was H-bonding between acidic
hydrogen (-COOH) and the fluoride ions.
The defluoridation capacity of protonated cross linked chitosan beads was investigated [65].

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This study was carried out in a similar way to the one mentioned before. The maximum
adsorption capacity was 7.32 mg g-1( 303K). The adsorption process was spontaneous and

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endothermic. The rate of reaction followed non linear pseudo- second order and intra-particle
diffusion kinetic models. The sorption mechanism suggested was H-bonding between protonated

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amine groups (NH3+) and F- ions. Viswanathan et al. [69] also studied the defluoridation
capacity of chemically modified chitosan beads by introducing NH3+ and COOH groups by

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means of chitosan protonation and carboxylation.

5.2 Electropositive multivalent metals incorporated to chitosan beads

Fluoride ion is classified as a hard base due to its high electronegativity and small ionic size

and presents strong affinity for electropositive multivalent metal ions like transition and rare
earth metals (Al (III), Fe (III), Ti (IV), La (III), Zr (IV), Ce (III), etc. As rare earth metals are

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expensive, a number of researchers have loaded these metals on cheaper components as chitosan
supports to enhance adsorption capacity and to diminish the adsorbent cost.

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It is a well known fact that the N in the NH2 group of chitosan acts as an electron donor and it
is responsible for selective chelation with metal ions (La 3+, Ce 4+, Fe 3+, Ti 4+, Al 3+, etc) [50-51].
These metal ions complete their coordination shells with OH groups, that can bind or release H+
depending on the solution pH. Under acidic conditions, the OH groups are protonated and can
adsorb F- ions through exchange mechanism. At acid pH, the fluoride sorption capacity is
diminished probably due to formation of HF and at alkaline pH values, fluoride sorption also is
lower due to competition with OH- ions.
Results on F- adsorption onto chitosan composites from different researchers are shown in
Table 1.
5.2.1. Mg
Magnesia (MgO) is a well known adsorbent with high defluoridation capacity. In order to
overcome the limitations of MgO for field application, Sundaram et al. [45] used a composite
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magnesia/chitosan (MgOC) for F- removal from aqueous solution. Equilibrium data fitted
Langmuir and Freundlich isotherm, the maximum adsorption capacity for F- removal was 11.24
mg g-1 (303K). Evaluation of the thermodynamic parameters suggested the spontaneous and
endothermic nature of the adsorption process. The kinetics of F- adsorption onto MgOC followed

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pseudo-second order model and particle and intraparticle diffusion models. The adsorption
mechanism suggested was ion exchange. Since the pHzpc of MgOC is 10.6, the adsorbent was

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positively charged up to this pH value; hence the adsorbent was able to remove F- ions by
electrostatic attraction for a wide pH range. Also, chitosan could also contribute to the F-

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adsorption capacity by removing F- ions through hydrogen bonding.

5.2.2. Al

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Aluminum impregnated chitosan (AIC) was prepared and applied as an adsorbent for the
removal of F- ions form aqueous solution [47]. Batch adsorption experiments on AIC were

carried out at different pH, contact time, dose, presence of diverse anions and initial fluoride
concentration to determine the optimum adsorption conditions. Experimental data were fitted to
Langmuir and Freundlich isotherms. The maximum adsorption capacity for F- ions onto AIC

was 1.73 mg g-1. The adsorption process followed first order Lagergren model kinetics.

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Thermodynamic parameters suggested that the adsorption process was spontaneous and
endothermic in nature. At low pH values, the surface of the adsorbent was positively charged and

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F- was removed by exchange process. The AIC adsorbent could be regenerated at pH 12.
In order to improve the adsorption capacity of alumina, alumina/chitosan composite (AlCs)
was prepared by incorporating alumina particles in the chitosan polymeric matrix [56]. The
effect of different experimental parameters was studied and adsorption equilibrium data were
fitted to Langmuir and Freundlich isotherms. The maximum F- adsorption capacity was 10.42
mg g-1. Thermodynamic parameters suggested that the adsorption process was spontaneous and
endothermic in nature. Kinetic studies determined that the process followed pseudo-second order
and particle and intraparticle diffusion models. The fluoride removal by AlCs composite was
mainly governed by electrostatic adsorption and complexation mechanisms.
5.2.3. Fe

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Fluoride removal by Fe (III) loaded carboxylated chitosan beads (Fe-CCB) was investigated
[50]. Batch experiments were carried on under different experimental conditions, pH, contact
time, initial fluoride concentration, adsorbent dose, presence of competitor co-anions, etc.
Experimental data were fitted to Langmuir and Freundlich isotherms. The fluoride maximum

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adsorption capacity was 15.38 mg g-1 (303 K). Thermodynamic parameters suggested the
spontaneous and endothermic nature of the adsorption process. Kinetic studies were carried on

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with reaction-based and diffusion based models. The pseudo second order model and the
intraparticle model were the best fit for experimental data. The main sorption mechanism
electrostatic attraction between chitosan-COO-Fe

3+

3+

ions and

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proposed was complexation through chitosan-NH2 groups chelated with Fe

groups and fluoride ions, whereas with

carboxylated chitosan beads, the adsorption mechanism was only H-bonding between HCOO-

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chitosan groups and fluoride ion.

5.2.4. Ti

The metal binding property of chitosan was used to incorporate Ti metal and applied as an
adsorbent for fluoride removal [47]. The influence of different experimental parameters such as

pH, initial F- concentration, adsorbent dose, and presence of coexisting anions was investigated.

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Experimental data were fitted to Langmuir and Freundlich isotherms. The maximum adsorption
capacity was 7.21 mg g-1. Thermodynamic parameters indicated that the adsorption process was

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spontaneous and endothermic. The authors concluded that the mechanism of adsorption of
fluoride was complex and that surface adsorption and also intra- particle diffusion contributed to
the rate determining step. The adsorption mechanism was ionic exchange between OH- from
chitosan-Ti-OH groups (Ti (IV) coordinated with chitosan through NH2 groups) and F- ions.
5.2.5. Ti-Al

The performance of Ti-Al binary metal oxide supported beads using chitosan template was
studied for fluoride removal from drinking water [49]. The higher removal capacity of the
synthesized adsorbent (Q max = 2.22 mg g-1) compared to bare chitosan was due to higher surface
area. The effect of different experimental parameters on F- adsorption on the adsorbent was
investigated. The experimental data were fitted to Langmuir and Freundlich adsorption models
and to pseudo-second order and intra-particle diffusion kinetic models. The adsorption process
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was spontaneous and exothermic in nature. It was observed that multiple treatments with 2%
alum (KAl(SO4)2.12H2O) solution regenerated 80 % of the adsorbent. The effect of flow rate on
fluoride adsorption capacity was also studied in column experiments.

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5.2.6. SiO2

Chitosan coated silica (CCS) was used for defluoridation of aqueous solution [74]. The effect
concentration was investigated through batch experiments.

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of experimental parameters such as pH, contact time, adsorbent dose and initial fluoride
Adsorption data were fitted to

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Langmuir and Freundlich isotherms. The maximum adsorption capacity was 44.4 mg g-1. The

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kinetic studies indicated that F- sorption onto CCS followed pseudo-second order kinetics.
5.2.7. La

Kamble et al. [42] investigated the effects of different parameters (pH, adsorbent dose, initial

F- concentration, the presence of interfering ions) on the adsorption of F- by chitin, chitosan and
chemically modified La-chitosan (20 % of La loading). The authors concluded that the Fremoval capacity and affinity of 20 % La-chitosan was higher than that of chitin and chitosan.

The presence of anions, particularly carbonate and bicarbonate diminished F- adsorption.

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Experimental adsorption data fitted Freundlich isotherm and Lagergren first-order model. It was
concluded that the mechanism of F- removal by 20 % La-chitosan was complex and both the

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surface adsorption and the intra-particle diffusion contributed to the rate determining step.
Viswanathan and Meenakshi [51] investigated the defluoridation capacity of La-carboxylated
chitosan beads (La-CCB). The adsorption experimental data were fitted to Langmuir and
Freundlich isotherms. The authors reported that the maximum F- adsorption capacity of La-CCB
was 11.905 mg g-1 (303 K) almost 3 times higher than the one of carboxylated chitosan beads.
Thermodynamic parameters suggested the spontaneous and endothermic nature of the adsorption
process. The kinetic studies were carried on with reaction-based and diffusion based models. The
pseudo second order model and both the particle and intraparticle model were the best fit for
experimental data. The authors suggested that La-CCB removed F- ions by complexation through
NH2 chitosan groups chelated with La

3+

ions. In addition there is a possibility of exchange of

La3+ ion for H+ ion in carboxyl group of chitosan, which contains oxygen atom acting as an

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electron pair donor to the Lewis acid (La

3+

) followed by electrostatic attraction between

chitosan-COO-La 3+ groups and fluoride ions.

Synthesis of lanthanum incorporated chitosan beads (LCB) and its application for the
removal of F- ions from groundwater was also investigated by Bansiwal et al. [66] and Thakre et

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al. [48]. The synthesis was optimized by varying different parameters such as lanthanum loading,
complexation and precipitation time, concentration of ammonia solution used for precipitation,

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etc. The effect on the adsorption capacity of pH, adsorbent dose, initial F- concentration,
presence of other anions and cations was investigated. La-chitosan beads showed fluoride

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removal efficiency of 97 % at pH5. The presence of other anions affected the fluoride uptake.
The maximum adsorption capacity was 4.7 mg g-1. Adsorption data fitted Langmuir isotherm.
The kinetics of the adsorption process was rapid and data followed pseudo-first order kinetics.

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The authors concluded that the adsorption of fluoride process was complex and involved surface
adsorption and also inter and intra-particle diffusion. Thermodynamic parameters suggested that

the adsorption process was spontaneous and endothermic. The fluoride loaded material could be

5.2.8. Zr

regenerated after complete saturation with NH4Cl 1 M (81.22 % regeneration capacity).

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Zr (IV) loaded carboxylated chitosan beads (Zr-CCB) was synthesized and fluoride removal
studies were carried out in batch experiments under different experimental conditions [52]. The

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effect of pH, contact time, initial fluoride concentration, competitor anions, was investigated.
The adsorption data were fitted to Langmuir, Freundlich and Dubinin-Radushkevich (D-R)
isotherms. The maximum adsorption capacity was 13.699 mg g-1 (303K). The fluoride
adsorption process was spontaneous and endothermic as G and H values were negative and
positive respectively. No kinetic studies were reported. The mechanism proposed was similar to
that proposed for La-CBB mentioned before.
A new biocomposite was prepared by incorporating Zr (IV) tungstophosphate, an inorganic
ion exchanger into chitosan biopolymeric matrix [54]. The adsorption of F- ions on this
biocomposite was investigated by batch technique. The influence of pH, contact time, initial Fconcentration, competing co-ions and temperature in the adsorption process was investigated.
The equilibrium adsorption data were fitted to Langmuir and Freundlich isotherms, the
maximum adsorption capacity was 7.63 mg g-1. The kinetics of the adsorption process followed
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pseudo-second order and intra-particle diffusion models. The thermodynamic parameters

suggested the spontaneous and endothermic nature of the F- adsorption.
5.2.9. Ce

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Chitosan modified by carboxylation followed by chelation with Ce (III) was investigated as

and adsorbent for F- removal from aqueous solution [53]. Experimental batch studies were

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conducted under different pH, contact time, presence of competitor co-anions. The experimental
data were fitted to Freundlich and Langmuir isotherms. The maximum adsorption capacity was

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9.00 mg g-1. Thermodynamic parameters confirmed the spontaneous and endothermic nature of
the adsorption process. The kinetic data were fitted to reaction and diffusion based models. The
pseudo-second order and intra-particle diffusion models were the more significant in defining the

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fluoride sorption process. The mechanism proposed was similar to that for La-CCB mentioned

before.
5.2.10. Nd

The applicability of neodymium-modified chitosan as F- adsorbent from aqueous solution was

studied [75]. The effect of temperature, adsorbent dose, particle size and the presence of co-ions

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on the adsorption process was investigated. The experimental data were fitted to Langmuir and
Freundlich isotherms. The maximum adsorption capacity was 11.41 mg g-1 (283K). Sorption

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studies revealed that the pseudo-second order was suitable to describe the F- adsorption process
onto the adsorbent. The process was complex, and both the boundary of liquid film and intraparticle diffusion contributed to the rate determining step. The adsorbent was regenerated in 24 h
by a 4 g L-1 NaOH solution.

5.3. Chitosan biocomposites

The development of polymeric composite materials in which the combination of the

properties of the constituents lead to an increase of the functional or structural properties of the
composite material is of great interest. The composites based on biodegradable materials have
received more attention because they are environmentally friendly.

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Nano hydroxyapatite (n-HAp) was found to have high defluoridation capacity (Q

max

= 3.113

mg g-1) and also low cost and availability [77]. However when n-Hap powder has been used as
such, it causes significant pressure drop during filtration and this disadvantage out weights its
advantage of higher F- removal. In order to overcome this problem, n-Hap was made into a

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biocompatible biocomposite with chitosan which could be made into any desirable form [43].
Batch experiments were carried on to study the influence of different experimental parameters on

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the F- adsorption by the composite material. Data were fitted to Langmuir and Freundlich
isotherms; the maximum adsorption capacity was 2.040 mg g-1 (30C). The adsorption process

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was spontaneous and endothermic. The rate of sorption followed pseudo-second order kinetic
model and occurred through pore diffusion. The main mechanism responsible for F- adsorption
onto the biocomposite material was electrostatic attraction between the positive surface and

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negatively charged fluoride ions. Similar studies were carried on using nano-hydroxyapatite
/chitin composite [44]. The maximum adsorption capacity was 8.41 mg g-1 higher than that of n-

HAp/chitosan. The authors suggested that the enhancement of the defluoridation capacity with
respect to n-Hap might be due to biosorption by chitin, adsorption by physical forces and

fluoride ion entrapped in fibrilliar capillaries and spaces of polysaccharide network of the chitin
moiety, but they didnt explain the different defluoridation capacity between chitosan a chitin

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biocomposites.

The optimum composition of a chitin based biocomposite was determined based on both its

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fluoride adsorption capacity and it is chemical resistance in acid aqueous solution [41]. Chitin
content, polyurethane polymer content, catalyst content, chitin particles size, degree of
acetylation of chitin and effect of pH on the F- adsorption was investigated. No isotherm or
kinetic studies were carried on. The optimized biocomposite adsorbed 0.29 mg g-1 at F- initial
concentration of 15 mg L-1 and pH 5.0.
The hydrotalcite (HT) adsorption capacity was enhanced by preparation of HT/ chitosan
composite [55]. Hydrotalcite is a layered doubled hydroxide with a general formula [M
3+

(OH)2]

x+

[A

n-

x/n

.m H2O ]

x-

where M

2+

and M

3+

2+

1-x

are di- and trivalent metal cations and A

is an interlamellar anion with charge n-. Fluoride adsorption experiments were carried on under
different experimental conditions. Experimental data were fitted to Langmuir and Freundlich
isotherms. The fluoride maximum adsorption capacity was 1.876 mg g-1 (30C) and increased
with temperature. The F- removal process was spontaneous and endothermic. Adsorption data
13
Page 13 of 30

were best fitted to pseudo-second order and intra-particle diffusion kinetic models.

The

adsorption mechanism suggested was ion exchange between counter ions at positive surface sites
on HT and chitosan, and also the exchange of interlayer anions of HT and structural hydroxyl

ip
t

groups of the HT layers.

cr

5.4. Magnetic chitosan particle

A magnetic chitosan particle was prepared by the co-precipitation method with Fe 2+ and Fe 3+

us

solutions (ratio Fe 3+/Fe 2+ = 3:2), and employed to remove F- ions from water solution [70]. The
two sites Langmuir isotherm and Bradleys equation were fitted well with the experimental
adsorption data. Maximum adsorption capacity reported was 22.49 mg g-1. Results from

an

Dubinin-Radushkevich (D-R) isotherm suggested that the adsorption was physical as Ea was 2.48
kJ mol-1. Adsorption data fitted pseudo-second order kinetic model. The authors suggested that

the principal adsorption mechanism was F- physical interaction with the NH2 and Fe-O groups on

the surface of the magnetic particle.

te

5.5 Comparison of sorbent effectiveness of chitosan derivatives and composites

It has to be mentioned that the F- maximum adsorption capacity of different adsorbents

Ac
ce
p

reported in Table 1 gives us some idea of sorbent effectiveness, as it depends on experimental

conditions (pH, temperature, dose, ionic strength, particle size, presence of competing ions etc).
Generally the adsorption capacity of an adsorbent increases with increasing F- initial
concentration until saturation conditions. The isotherm studies performed for a higher range of
fluoride concentrations will show higher capacity than those of lower ranges and the maximum
adsorption capacity obtained from Langmuir isotherm will differ in both cases [78], so it is
important to take into consideration the initial fluoride concentration range, when performing
comparative studies. Fluoride concentration in ground waters of the worst affected countries like
India are in the range of 0.5-48 mg L-1. Nonetheless, it is not uncommon to encounter isotherm
studies performed at fluoride concentration of 1000 mg L-1 [79] and even up to 2500 mg L-1[17].
In most of the papers reviewed the isotherm studies are carried on by varying the initial
concentration of the F- solution. But in groundwater, the F- concentration remains constant, so it
14
Page 14 of 30

seems more representative of natural waters to run isotherm studies on dose-variation of

adsorbents instead of studies on fluoride concentration variation [78].
It has to be taken into account that some of the adsorbents reported presented high adsorption
capacity at high F- equilibrium concentration in water, but, in water treatment, the final

ip
t

concentration of F- in the water solution must be below 1.0 mg L-1. So it is desirable that the
adsorbent presents high adsorption capacity at low fluoride equilibrium concentrations. The F-

cr

adsorption capacity corresponding to F equilibrium concentration 1.0 mg L-1 is seldom reported,

but can be calculated from isotherm equations. As seen in Fig.1, the best F- adsorbents reviewed

us

in this paper were Nd-chitosan and MgO-chitosan followed by rare earth metal-chitosan
derivatives because they presented higher adsorption capacity at the equilibrium F- concentration

an

of 1 mg L-1.

6. Comparison between chitosan and other low cost adsorbents performance

A research of the recent literature has already been conducted on fluoride sorption by a wide
variety of low cost adsorbents. Results on the fluoride sorption performance by alumina and

alumina based materials, clays and soils, calcium based minerals, metal oxides, carbon based

te

materials and synthetic materials are listed on Table 2.

Although as noted before, the maximum adsorption capacity is reported in this paper only to

Ac
ce
p

give some idea of sorbent effectiveness, a comparison between results reported in Tables 12
shows that chitosan derivatives, mainly at the right extreme of Fig 2, present good F- removal
capacities, only surpassed by Al-Ce hybrid, Ce (IV) oxide/SiMCM and Fe-Al-Ce trioxide. We
have already mentioned that rare earth metals have strong affinity to fluoride. As they are very
expensive, usually they are mixed with cheaper materials to reduce costs and maintain the high
fluoride adsorption capacity. In the case of the Al-Ce hybrid adsorbent, the pHZCP 9.6 results in
fluoride adsorption on the positive adsorbent via electrostatic interaction. The hydrated
cerium(IV) oxide on the surface of SiMCM-41 has a high affinity for the fluoride ion, being the
adsorption mechanism anion exchange between the hydroxyl groups existing on the surface of
(Ce)SiMCM-41 and F- ions. In the trioxide, the aluminum oxide which has a pHZPC near 8.0
contributes to a high performance.

15
Page 15 of 30

Many times, chemically modification of different materials increases the adsorption capacity,
but the technology cost must be taken in consideration in order to produce real low-cost
adsorbents.

ip
t

6. Conclusions

Performance comparison of different low-cost adsorbents is difficult because of

cr

inconsistencies in data, principally due to different experimental conditions (pH, temperature,

ionic strength, particle size, range of initial fluoride concentration, presence of competing ions,

us

etc). Cost information is seldom reported in the publications because it depends on local
availability and on the technology applied.

an

In this paper, a recent literature review of F- adsorption by chitosan and by chemical

modified chitosan is presented. In a great number of papers reviewed the experimental data of

the F- adsorption process have been fitted to Langmuir or to Freundlich models. Regeneration
and reusing of the chitosan derivatives and composites is reported when it is possible. Chitosan
derivatives and composites present fluoride maximum adsorption capacity ranging from 1.39 mg

g-1 for raw chitosan [76] to 44.4 mg g-1 for chitosan coated silica [74]. The effect of competitive

te

anions, in particular carbonate and bicarbonate ions, is an important issue that needs to be more
studied as they decrease the fluoride adsorption capacity of chitosan derivatives.

Ac
ce
p

The use of chitosan composites and derivatives for removing F- ions from contaminated
solutions presents many attractive features such as the high adsorption capacity and the fact that
chitosan is obtained from natural raw sources (crustacean shell waste), an environmentally
friendly material of low cost, instead of derived from petroleum based materials. Nevertheless,
there are also disadvantages in the use of chitosan or chitosan derivatives. Some of them are the
fact that chitosan in flakes or powder is a crystallized polymer, so adsorption takes place in the
amorphous region of the crystals, limiting the adsorption capacity. Chitosan beads have reduced
crystallinity but they are soluble in acidic media. In the other hand, crosslinked chitosan
derivatives, generally insoluble in acidic and alkaline solutions, show a decrease in the fluoride
adsorption capacity as amino functional groups involved in crosslinking are not available for
ionic exchange with fluoride ions.

16
Page 16 of 30

Despite the fact that chitosan composites show good performance, more studies are needed to
transfer the process to industrial scale. Also, regeneration studies need to be performed in more
extent to recover the adsorbent, enhancing the economic feasibility of the process.
The versatility in possible chitosan derivatives let us predict that the F- sorption performance

ip
t

(equilibrium uptake and removal kinetics) and also the selectivity towards F- ions can be yet

cr

enhanced.

us

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21
Page 21 of 30

Figure captions
Fig. 1. Fluoride removal capacity by different chitosan derivatives and composites (Ce = 1.0 mg
L-1).

Ac
ce
p

te

an

us

cr

ip
t

Fig. 2. Comparison of maximum adsorption capacity of different fluoride adsorbents.

22
Page 22 of 30

Figure 1

9
8

Ce= 1.0 mg L-1

6
5
4
3

ip
t

Q (mg g-1)

2
1

Ac
ce
p

te

an

us

cr

Page 23 of 30

ed

ce
pt

Ac

100

150

cr

us

50

M
an

MnO2 coated activated alumina

quartz
activated and MnO2 coated
plaster of Paris
calcite
activated alumina
laterite
activated alumina
Fe acitvated quartz
chitosan
Al impregnated chitosan biopolymer
synthetic siderite
fluorspar
Al- impregnated C
hydrotalcite/chitosan composite
nano hydroxyapatite-chitosan
Ti-Al binary metal oxide supported
Mg bentonite clay
alfa alumina
aligned C nanotubes
MnO coated alumina
La-impregnated silica gel
Ti rich bauxite
10 % La-bentonite
carbon slurry
hydroxyapatite
La -chitosan beads
La- chitosan beads
alum sludge
multifunctional cross-linked
activated red mud
alumina
Ti-chitosan spherical beads
protonated cross-linked chitosan
chitosan supported Zr (IV)
polyacrilamyde Ce (IV)-PO4 resin
nano hydroxyapatite-chitin composite
polyacrilamyde Zr (IV)-PO4 resin
Ce(III) encapsulated chitosan
alumina cement granules
alumina/ chitosan composite
polyacrilamyde Al (III)-PO4 resin
carboxylated crosslinked chitosan
magnesia- chitosan composite
neodymium-modified chitosan
bone char
La(III) carboxylated chitosan beads
activated alumina
mixed rare earth oxides
Zr(IV) entrapped chitosan
mesoporous alumina
Fe(III) carboxylated chitosan beads
hydrous ferric oxide (HFO)
activated Ca-charcoal (650 C)
magnetic chitosan particles
La-impregnated crosslinked gelatin
C nanotube supported alumina
Zr (IV) impregnated collagen fiber
chitosan coated silica
La-exchanged zeolite F-10
Al-Ce hybrid adsorbent
Ce(IV) oxide/SiMCM-41
Fe-Al Ce trioxide

Q max (mg g-1)

200

ip
t

Figure 2

Page 24 of 30

ip
t

Table 1(I)

g )

pH optimal

type of
study

chitosan

1.39

6.0

multifunctional cross-linked
chitosan beads

7.32

6.25

Mg-chitosan

magnesia- chitosan composite

11.24

7.0

7.0

3.0-11.0

Ac

Al-chitosan
Al impregnated chitosan
biopolymer

7.0

alumina/ chitosan composite

1.7316

10.417

6.5

7.0

themodynamics

adsorbent
characterization

L,F

reference

[76]

spontaneous,
endothermic

SEM,EDX,FTIR

[67]

L,F

pseudo second
order, intraparticle
diffusion

spontaneous,
endothermic

electrostatic
adsorption

SEM,EDX,FTIR

[68]

L,F

non linear pseudo

second order,
intraparticle
diffusion

spontaneous,
endothermic

electrostatic
adsorption

SEM,EDX,FTIR

[69]

E,K,T

L,F

pseudo second
order, particle and
intraparticle
diffusion model

spontaneous,
endothermic

electrostatic
attraction; H
bonding

FTIR

[45]

E,K,T

L,F

Lagergren first
order

spontaneous,
endothermic

electrostatic
attraction

SEM,EDX

[47]

L,F

pseudo second
order, particle and
intraparticle
diffusion

spontaneous,
endothermic

electrostatic
adsorption,
complexation

SEM,EDX,FTIR

[56]

E,K,T

E,K,T

L,F

pseudo second
order, intraparticle
diffusion

ed

protonated cross-linked chitosan

beads

11.11

kinetic model

mechanism
proposed

electrostatic
adsorption and
Lewis acid-base
interaction

ce
pt

carboxylated crosslinked chitosan

beads

Isotherm

us

adsorbent material
chitosan and chitosan
derivatives

-1

M
an

Qmax (mg

cr

Table 1
Fluoride adsorption by chitosan derivatives and composites

E,K,T

E,K,T

Page 25 of 30

ip
t

Table 1(II)

cr

Table 1 (II) (continued)

Fe-chitosan

15.385

7.0

E,K,T

pseudo second order,

intraparticle diffusion

spontaneous,
endothermic

electrostatic
adsorption,
complexation

SEM, FTIR

[50]

L,F

Lagergren ,
intraparticle diffusion
model

spontaneous,
endothermic

anion exchange
between Ti-OH
and F

XRD,SEM,
FTIR,BET

[47]

L,F

pseudo second order,

intra-particle
diffusion model

spontaneous,
exothermic

electrostatic
attraction

SEM, XRD,
FTIR

[49]

ion exchange

SEM,XRD,FT
IR,TGA

[74]

electrostatic
adsorption,
complexation

SEM,EDX,FTI
R

[51]

XRD,SEM,
EDX,FTIR,BE
T

[42,66]

XRD

[48]

SEM,EDX,FTI
R

[52]

L,F

Ti-chitosan spherical beads

7.2

7.0

M
an

Ti-chitosan

E, K,T

Ti-Al chitosan

Ti-Al binary metal oxide

supported chitosan beads

2.22

3.0-9.0

E,K,T

44.4

E,D,K

La(III) carboxylated chitosan

beads

11.905

4.7

La- chitosan beads

4.7

Zr-chitosan
Zr(IV) entrapped chitosan
polymeric matrix

7.0

5.0

Ac

La -chitosan beads

13.699

L,F

pseudo second order

L,F

pseudo second order,

particle and
intraparticle diffusion

spontaneous,
endothermic

E, K,T

L,F

Lagergren , inter and

intraparticle diffusion
model

spontaneous,
endothermic

L,F

ce
pt

La-chitosan

ed

SiO2-chitosan
chitosan coated silica

7.0

us

Fe(III) carboxylated chitosan

beads

E,K,T

E,T

L,F,D-R

spontaneous,
endothermic

anion exchange
between La-OH
and F
electrostatic
attraction
electrostatic
adsorption and
complexation

Page 26 of 30

Table 1(III) continued

7.634

3.0

E,K,T

L,F

pseudo second order,

intraparticle diffusion

L,F

pseudo second order,

intraparticle diffusion

Ce- chitosan

9.00

7.0

E,T

Nd-chitosan

neodymium-modified
chitosan

spontaneous,
endothermic

M
an

Ce(III) encapsulated chitosan

polymeric matrix

spontaneous,
endothermic

us

chitosan supported Zr (IV)

tunsgtophosphate composite

cr

ip
t

Table 1(III)

L,F

pseudo second order,

boundary layer and
intraparticle diffusion

adsorption,
complexation, ion SEM,EDX,F
exchange
TIR

[54]

electrostatic
adsorption and
complexation

SEM,EDX,F
TIR

[53]

ion exchange

FTIR

[75]

11.41

7.0

E,K

nano hydroxyapatite-chitosan
composite

2.04

3.0

E,K,T

L,F

pseudo second order,

pore diffusion model

spontaneous,
endothermic

chemiosorption
and ion exchange

[43]

nano hydroxyapatite-chitin
composite

8.41

3.0

E,K,T

L,F

pseudo second order,

pore diffusion model

spontaneous,
endothermic

chemiosorption SEM, EDX,

and ion exchange
FTIR

[44]

hydrotalcite/chitosan
composite

5.0

1.876

magnetic chitosan

20.96-23.98

[41]

3.0

E,K,T

L,F

pseudo second order,

intraparticle diffusion

7.0

E,K

L, 2-sites L, B,
F,D-R

pseudo second order

Ac

magnetic chitosan particles

ce
pt

chitin-biocomposite

ed

chitosan-composites

spontaneous,
endothermic

SEM,EDX,F
TIR

[55]

physical (Van der SEM, XRD,

Waals)
FTIR

[70]

ion exchange

E; equilibrium; K: kinetic; D: dynamic; T: thermodynamic

L: Langmuir; F: Freundlich; D-R: Dubinin-Radushkevich; B: Brunauer isotherms
X-ray diffraction (XRD); scanning electron microscopy (SEM); scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX); Fourier transform infrared
spectroscopy (FT-IR ), thermogravimetric analysis (TGA)

Page 27 of 30

reference

quartz
MnO2 coated activated alumina
activated and MnO2 coated tamarind fruit
plaster of Paris
calcite
activated alumina
laterite
activated alumina
Fe acitvated quartz
synthetic siderite
fluorspar
Al- impregnated C
Mg bentonite clay
alfa alumina
aligned C nanotubes
MnO2 coated alumina
La-impregnated silica gel
Ti rich bauxite
10 % La-bentonite
carbon slurry
hydroxyapatite
alum sludge
activated red mud
alumina
polyacrilamyde Ce (IV)-PO4 resin exchanger
polyacrilamyde Zr (IV)-PO4 resin exchanger
alumina cement granules
polyacrilamyde Al (III)-PO4 resin exchanger
bone char
activated alumina
mixed rare earth oxides
mesoporous alumina
hydrous ferric oxide (HFO)
activated Ca-charcoal (650C)
La-impregnated crosslinked gelatin
amorphous alumina supported on C nanotubes
Zr (IV) impregnated collagen fiber
La-exchanged zeolite F-10
Al-Ce hybrid adsorbent
Ce(IV) oxide/SiMCM-41
Fe-Al Ce trioxide
MgAl-CO3 layered double hydroxides

[20]
[80]
[81]
[82]
[20]
[8]
[83]
[13]
[20]
[84]
[20]
[85]
[86]
[87]
[14]
[13]
[88]
[11]
[89]
[90]
[20]
[91]
[92]
[5]
[93]
[93]
[78]
[93]
[16]
[88]
[94]
[5]
[79]
[95]
[96]
[97]
[98]
[99]
[19]
[100]
[101]
[17]

Ac
ce
p

te

us

an

0.19
0.17
0.22
0.34
0.39
0.74
0.85
1.08
1.16
1.77
1.79
1.80
2.26
2.73
2.85
2.85
3.80
3.80
4.24
4.31
4.59
5.39
6.29
6.36
7.75
8.55
10.22
10.87
11.90
12.10
12.50
14.26
16.50
19.05
21.28
24.15
41.42
45.15
91.40
114.40
195.0
319.80

cr

Table 2
Fluoride maximum adsorption capacity on different materials
Q max (mg g-1)
adsorbent material

ip
t

Table 2

Page 28 of 30

*Graphical Abstract - Pictogram

9
8

Ce= 1.0 mg L-1

6
5
4
3

ip
t

Q (mg g-1)

2
1

Ac
ce
p

te

an

us

cr

Page 29 of 30

*Graphical Abstract - Synopsis

Some of the adsorbents reported in this paper presented high adsorption capacity at high Fequilibrium concentration in water, but, in water treatment, the final concentration of F- in the
water solution must be below 1.0 mg L-1. So it is desirable that the adsorbent presents high
adsorption capacity at low fluoride equilibrium concentrations. The pictogram shows that the

ip
t

best F- adsorbents were Nd-chitosan and MgO-chitosan followed by rare earth metal-chitosan
derivatives because they presented higher adsorption capacity at the equilibrium F- concentration

Ac
ce
p

te

an

us

cr

of 1 mg L-1.

Page 30 of 30